Method of preparing aliphatic oxyamines



I Patented air. 27,, 1945 Uii'ED STATES" PATENT OFFICE,

METHOD OF ALIPHATIC OXYAMINES Erwin L. Carpenter, OldGreenwiclt, Conn, as

signor to American Cyanamid Company, New

York, N. Y., a corporation of Maine No Drawing. Application October 4, 1941,

Serial No. 413,643

5 Claims. (yoi. 260584) The present invention relates to a method of preparing an aliphatic oxyamine of the formula wherein R is an aliphatic hydrocarbon radical, R. is a member of the class consisting Of hydrogen and an aliphatic hydrocarbon radical, and R is a member of the class consisting of hydrogen and the radical H R n R O t t It It 1'1 from a solution of an aliphatic oxynitrile containing an alkaline material, which includes the steps of first neutralizing said alkaline material and then hydrogenating the oxynitrile in the presence of a hydrogenation catalyst, and without removing the product of the neutralization reaction.

It has been found that the above class of amines may be obtained in an advantageous manner and with high yields as follows:

(1) Formation of the corresponding aliphatic oxymtrile by causing an nip-unsaturated nitrile having the formula bo-cz r:

in which R is either hydrogen or analiphatic hydrocarbon radical, to react with an aliphatic alcohol in the presence of a soluble alkaline catalyst;

(2) Neutralization of the alkaline catalyst-in the reaction product bv addition of the requisite amount of a concentrated mineral acid, and,

(3) Hydrogenation of the oxynitrile without removing the product of the neutralization reaction, preferably under elevated pressure in the presence of a'hydrogenation catalyst.

In the formation of the aliphatic oxynitrile an etherlinkage occurs in the molecule resulting from the addition of'the alcohol to the nitrile. For example, methyl alcohol may be readily added to acrylonitrile to form -3-methoxypropionitrile according to the equation:

* The aliphatic alcohols which may be used in,

forming the aliphatic oxynitriles includes the monohydric'primary, secondary, tertiary and unsaturated alcohols.

Solubl alkaline catalysts which may be utirange of 70-l'7 5 C., and at increased lized in promoting the reaction between the (1,19- unsaturated nitrile and the aliphatic alcohol include the metal alcoholates (e. g. NaOCHa, KOCHa, NaOCaHs, KOCaHs and the like), the oxides and hydroxides of those metals which are soluble in aliphatic alcohols (e. g. NaOH, KOH,

- NaQO, K). The alcoholates may be introduced into the reaction mixture per se, or they may be formed in the reaction mixture. in situ, for instance' by adding a metal such as sodium or potassium, a metal amide (NaNHz), a metal urea and the like. The amount of said catalyst utilized is exceedingly small, and usually in the proportion of from .005 to 1% of the total weight of the nitrile and alcohol.

While the reaction between the cap-unsaturated nitrile and the aliphatic alcohol takes place in most mixtures at a temperature within the range of to 150 C., it may be found practical to aliphaticoxynitriles include metals such as nickel,

- ide. Usually it is preferable to employ the catacopper and cobalt, and difflcultly'reducible metal c oxides such asplatinum oxide and chromium oxlyst in a1finely divided form, and hence Raney nickel is found to be very eilicient.- In some cases it may be advantageous to use the catalyst in the form of grains or pieces, or it may be deposited on or dispersed in carriers such as zeolites, silica gel, pumice stone, bleaching earths, and the like.

By a proper selection of the hydrogenation con- V ditions, thatv is, temperature, pressure of hydrogen, type and quantity of catalyst used, either mainly primary or mainlysecondary amine is formed. High yields of primary amines are more readily obtained in a rapid reaction employing high hydrogen pressure. a relatively large amount of catalyst and as low a temperature aspossible.

High yieldsof primary amine are also ohteined other hand, a. slow reaction employing low hydrogen pressure with or without the use of on inert diluent gas such as nitrogen, a. relatively small amount of catalyst end 9. high temperature,

(ISO-250 C.) favors the formation of secondary amines. A large amount oi seeondery amine may also be formed, if desired, by sorptioh of'hydrogen et rather low temperatures (ill-fit? C.) followed by heath-us the mixture to considerably higher temperatures (Wt-300 C.) ior sever-ell hours in contact with hydrogen and the hydrogenetion catalyst.

During the hydrogenation it is mvunteeeous to mix the reacting materials thoroughly, tor exemple, by stirring or sloshing or the vessel. I v

These aliphatic oxyeminesheve as number oi widely diversified uses. -When combined with fatty acids they readily form. coups which valuable emulsifying agents suiteble for at number of purposes, forexempie, in the prepstrution of polishes, paints, lecuuers, printing compositions, waxes, leather dressings, paper costing, finishing compositions, water-proofing compositions, shoe creams and polishes, end in general, ell types oi film-forming emulsions. The free omiues may also serve as emulsifying scents in number oi cases.

I The presence of on other and an amine roup in the some molecule tends to increase both the oil and water solubility of, the products. The

lower members of the series ore completely nits cible with water as well us with oil of the common organic solvents. They sre good solvents s es,

deteii by the preparation of the compounds shown in the following examples. Ports indicated are by weight.

Emmpw 1 0.5 port of sodium rnetul is dissolved. in 135 parts or methyl alcohol. 212 parts of ecrylonitrile are .added slowl with stirring, the tempereture being maintained at Bil- C. by ,cool- The solution is stirred for three hours, then neutralized with the requisite amount of con- Eoample 2 159 parts of acrylonitrile are added. slowly with stirring to 195 ports of n-propyl alcohol in which is dissolved 0.3 port of metallic sodium, the wmperuture being held between 35 and C. throughout the addition. The resulting solution is stirred for five hours at room temperature, neutrulized with concentrated sulfuric acid and hydrogenated in contact with'lfl parts of Honey for resins, dyes, waxes, casein and shellac. The

longer members of the series, and in particular [C1aH31O(CH2)s]2NH, are excellent cation-octive softening usents for use in the tee field. The products or this invention may also be useful as wetting scents, detergents, demulsifiers and lubricants. They may be employed in breakiug petroleum emulsions, as o. solvent for gasoline, in the color stabilization of gasoline,

and lubricating oils; in pucotion procmses such as the removal end/or recovery of acid gases, for exemple hydrogeii sulfide, sulfur dioxide and carbon dioxide, in the neutralization of the ocidity of oils, in the preparation of cocelerstors, inhibitors, unti-oiddeuts, anti-ireese solutions and anti-knock agents, as corrosion inhibitors, insecticides, fly .sproy ingredients.

pharmaceuticals, fire proofing vscents, tanning sgents, foaming agents, and textile assistants, in improving dye compositions, in the preparation of pigments and lakes, us flotation re-- agents, plasticizers for paints and nitrocellulose lacquers, es alkaline materials for permanent wave solutions, in formulating dr ll-cleaning soups, cosmetic creams, and in general cleans ing compositions containin soaps.

These amines also serve as intermediates in the preparation of numerousderivatives such as, 7

for exemple, various salts by reaction with inorganic acids, N-substituted amides and imides,

' alkylated, arylated, hetero-substituted amines and their salts, N-halogenderivatives, alkyl dithiocarbamic acids, thionyl amines, nitroso amlnesrhydroxyemines, hydroxamic acids, substituted cyanamidcs, guanidines, melamines, ureas, Grig'nurd reagents, substituted alkylol amines, azides, sulfamic acids, sulfonemides, etc.

This invention will be illustrated in greater;

in vacuo.

nickel under a. pressure of 60-100 atmospheres at -120 C. The amines produced are filtered free or the nickel catalyst and fractionolly distilled to yield 228.2 ports of 3-,n-propoxypropylairline (boiling point of 84-89 C. at 80 mm.) and 75.6 ports of bis(3-n-propoxypropyl) amine (boilmg point of-94-98" C. at 0.5-1 mm. pressure).

Example 3 One part of sodium metal is dissolved in 188.7 ports of n-butyl alcohol. 132.5 parts of acrylonitrile are added slowly with stirring while the temperature is held at 40 C. The solution is stirred for six hours at room temperature and then neutralized with sulfuric acid. 15 parts of ey nickel are added. The mixture is hydnogen'ated in an autoclave under a pressure of 70-115 atmospheres at -125" C. The nickel catalyst is removed arid the product distilled (boiling point Eli-84 C. at, 30 mm.) and 69.6 parts of bis(3-n-butoxypropyl) amine (boiling point 115 C. at 0.5 mm.) are obtained.

Example 4 parts of 3-(2-ethylhexoxy) -propy1 amine (boiling point Vi-77 C. at 0.5 mm.) and 58.5 parts oi bis [3-(2-ethylhexoxy) -propyl] amine (boiling point 151-160 C. at 0.5 mm.)

Examplle 5 A mixture consisting of 5 parts of Honey nickel and 87.7 parts of crude 2-methyl-3-methoxypropionitrile (containing sodium sulfate resulting 218.2 parts of parts 0! B-n-butoxypropylamine from the neutralization of the sodium catalyst with sulfuric acid) is treatedat 110 C. in an autoclave with hydrogen. under a-pressure of -55 atmospheres as long as hydrogen is ab- Example 6 to homogenization or high speed agitation, as in a colloid mill, in order to prepare excellent semipermanent finishes that are well retained by the yarns and fabrics even after several washings.

A solution of 0.5 part of metallic sodium dissolved in 10 parts of ethyl alcohol is added to 270 parts of n-octadecyl alcohol heated to 60 C. To this solution 60 parts of acrylonitrile are added slowly with stirring, the temperature being held at approximately 60 C. by adequate cooling. After the addition of the nitrile, the solution is kept at 60-65 C. for 16 hours. It it then neutralized with concentrated sulfuric acid and treated at 105-110 C. in an autoclave with hydrogen under a pressure of 130 atmospheres in contact with 10 parts of Fancy nickel catalyst. After the hydrogenation is completed, the solution is cooled to 70-80 C., filtered from the nickel catalyst and evacuated to remove any ammonia formed during the reaction. The resulting product is a white waxy crystalline solid at room temperature consisting of approximately 75% 3-n-octadecoxypropylamine and 25 bis 3-n-octadecoxypropyl) amine.

Example 7 The auto- L are obtained which becomes a hard, crystalline solid when cooled to room temperature. This product consists of approximately 13% 3-n-octadecoxypropylamine and 87% bis(3-n-octadecoxypropyl) amine.

As noted above, many of the amines of the present invention, and particularly the higher amines,

are excellent textile finishingagents when used in the form of their salts. has been found that bis(3-n-octadecoxypropyl)-- Thus, for example, it Y Additional representative compounds that have shown excellent properties when used as textile finishes are bis(3-n-dodecoxypropyl) amine acetate and 3-n-octadecoxypropylamine acetate. In general, the mixture=' of primary and secondary amines formed in the hydrogenation may be used without any separation into the component parts.

These and similar aliphatic oxyamines may be used either in the form of their salts with inorganic acids such as the sulfate, hydrochloride, etc.,

oras salts of organic acids such as acetic, oxalic, tartaric, .a-hydroxyisobutyric acids .and the like.

While the invention has beende'scribed with particular reference tospecific. embodiments, it is to be understood that it is not to be limited thereto but is to be construed broadly and restricted solely by the scope 'of the appended claims.

This application is a continuation-in-part of applicant's application Serial No. 343,548,.

I claim:

1. A method of preparing an aliphatic oxy-'- amine 'of the formula wherein R is an aliphatic hydrocarbon radical, R" is a member ofthe class consisting of hydrogen and an aliphatic-hydrocarbon radical, and R is a member of the class consisting of hydrogen and the radical l\ a from a solution of an aliphatic nitrile of the ior-. mula containing an alkaline material selected from the group consisting of sodium alcoholateslpotassium' alcoholates, sodium hydroxide, potassium hydroxide, sodium oxide and potassium oxide, which includes the steps of'first neutralizing said alkaline material and then hydrogenating the oxynitrile in the presence of a hydrogenation catalyst, and

' without removing the product of the neutralizaamine acetate is an excellent cationic or so-called permanent finish for textile materials such as yarns, threads, cotton, silk, rayon and the like. Preferably the yarn or fabricis dipped .into or sprayed with a water solution or water dispersion of the amine salt of a sumciently high concentration to leave thereon, after drying, approximately 1% or less of the finish.

In addition to their-use as the sole finishing agents for textiles, the higher amines of the present invention may also be applied in the form of emulsions with fats, oils, waxes, urea-formaldehyde resins, alkyd resins paraflln, or mixtures containing the same. Many of the higher aliphatic oxyamines are excellent emulsifying I agents for fats, oils, waxes and resins, so .that it is only necessary to subject these substances in admixture with an-aqueous solution of the amine tion reaction.

2. A method of preparing an aliphatic oxy-' amine of the formula 1 H H H n v I wherein R. is an aliphatic hydrocarbon radical, R

is a member of the class. consisting of hydrogen and an aliphatic hydrocarbon radical, and R? is a member of the class consisting of hydrogen and the radical Y I R H from a solution of an; aliphatic nitrile of the formiila material with sulfuric acid and then hydmgenahing the oxynitrlle m the presence of a hydrogenation catalyst, anti without removing the pmduct of the neutralization reactioa.

3. The methad oi claim 1 in which the catalym w is Raney nickel.

@. The mama 012 mimi mwmh we hydro gena'igm is candied out M: from 7% C. to 360 under pressure.

, 5. The method of claim 1 in which the hirdrogenatina is can-1m mm at ram 70 C. to 300 C. under iwm 20 to mmca'pheres and in the presence of Bane nickel asa catalyst. 

